Curable compositions from blend of maleimido compound and vinyl ether

ABSTRACT

Solventless blends are provided of a maleimido methyl substituted toluene and a vinyl ether. The aforesaid solventless blends can be converted to high performance films when cured with ultraviolet radiation.

finite tates patent Schroeter Dec; 17, 1974 1 1 CURABLE COMPOSITIONSFROM BLEND [56] References Cited OF MALEIMIDO COMPOUND AND VINYL UNITEDSTATES PATENTS ETHER 2,997,459 1/1961 Schnell et a1. ..260/47 XA [75]Inventor: Siegfried H. Schroeter, Schenectady, 322L080 1 1/1965 FOX260/860 N Y 3,352,832 11/1967 Barr et a1. 260/78 UA 3,380,964 4/1968Grundschober et a1. 260/78 UA [73] Assignce; General Electric Company,3,413,379 1 1/1968 Schade et a1 260/78 UA Schenectady, NY. PrimaryIiraminer-Harold D. Anderson [22] Flled' 1973 Attorney, Agent, orFirmWilliam A. Teoli; Joseph T. {21] Appl. No.: 349,640

Related US. Application Data Division of Ser. No. 164,818, July 21,1971, Pat. No.

Colen; Jerome C. Squillaro [57] ABSTRACT Solventless blends are providedof a maleimido methyl substituted toluene and a vinyl ether. Theaforesaid solventless blends can be converted to high performance filmswhen cured with ultraviolet radiation.

3 Claims, No Drawings and (B) a vinyl ether of the formula, (2) CH=CHOY,

where there is utilized in such blends a proportion of (A) to (B) whichis sufficient to provide a ratio of maleimido radicals of (A), to vinylradicals of(B), having a value between 1 and inclusive, and preferably 1to 5, R is an alkylene radical, X is selected from hydrogen, alkyl,halogen and mixtures thereof, and Y is a monovalent organo radicaldefined below.

' Radicals included by R are preferably alkylene radicals such asmethylene, dimethylene, trimethylene, tetramethylene, substitutedalkylene radicals'such as m where m is an integer equal to l to 4inclusive, and R is selected from hydrogen, lower alkyl, such as methyl,and aryl, such as phenyl, Radicals included by .X are methyl, ethyl,chloro, fluoro, etc. Radicals included by Y are, for example, C,,,,,alkyl, such as methyl, etc., al-

kenyl, such as, l-propenyl, vinyl, allyl, etc.; hydroxyalkyl, such as,hydroxymethyl, hydroxyethyl, etc.; haloalkyl, such as, chloromethyl,chloroethyl, bromobutyl, etc., aryl such as phenyl, tolyl, xylyl, etc.;-R(OR)- ,,Z, where n is 1 to 100 and Z is selected from hydrogen,hydroxy, oxyalkyl such as oxymethyl, oxyethyl, ox ypropyl; oxyalkyenyl,such as oxyvinyl, oxyallyl, etc.

There are included by the maleimido substituted aromatic carbocyclicorganic materials having chemically combined radicals of formula 1,monomers and polymers such as bis(maleimidomethyl)toluene, bis(-maleimidomethyl)benzene, bis(maleimidomethyl)phenyl ether, etc.,maleimido'substituted aromatic carbocyclic polyethers, polyesters,polycarbonates, poly-amides, polyamide-imides, polyurethanes,polybiurets,

polyxylylene, polyarylacetylenes, polyarylsulfides, etc.,

consisting essentially of chemically combined units of the formula,

.2 where R is an aromatic 'carbocyclic radical having from 6 to 18carbon atoms, or a mixture of such units, with units having polyvalentaliphatic radicals in place of R radicals, a has a value ofO or 1, and yis an integer having a value of l to 500, and Z is a divalent connectiveselected from,

O O O O l u n n H R -CO-, -C-,'-O-, -OCO, -C-N-, -S-,

1 1 2 1 N-CO-, -N-C-NC-N-,

n n O O 0 1 1 R 1 n R R v R -S-. -N-,'CI-N-, -C-,

In addition, there also are included imido-alkylene substitutedpolystyrenes, poly(a-methylstyrene), polymethyl (a-methylstyrene),poly(dimethylstyreneL poly(chlorostyrene), poly(dichlorostyrene),styrene copolyme'rs with butadiene, acrylonitrile, methylmethacrylate,vinylidenechloride, maleic anhydride, vinylchloride, vinylacetate,vinylamides, a-methyls'tyrene, etc., included by the formula,

where R is a monovalent aromatic'carbocyclic radical having from 6 to 18carbon atoms selected from hydrocarbon radicals and halogenatedhydrocarbon radicals, R is selected from hydrogen and monovalenthydrolected from,

carbon radicals, and Z is a divalent connective sewhere Q is a divalentorgano radical Such as derived from R radicals defined above acrossthedouble bond. Radicals included by R are for example, phenyl, tolyl,xylyl, naphthyl, anth'ryl; chlorophenyl, chloronaphthyl, etc. Radicalsincluded by R, are R radicals, alkyl radicals such as methyl, ethyl,propyl, etc. D is selected from hydrogen and alkyl radicals, such asmethyl, etc.

There are included by the aliphatically unsaturated ethers of Formula 2,ethers such as, methyl vinyl ether, n-butyl vinyl ether, octyl vinylether, B-hydroxyethyl vinyl ether, triethylene glycol monovinyl ether,poly ethylene glycol mono vinyl ether, divinyl ether, tetraethyleneglycol divinyl ether, ,B-chloroethyl vinyl ether, phenyl vinyl ether,o-chlorophenyl vinyl ether, tolyl vinyl ether, benzyl vinyl ether,diethylene glycol vinyl allyl ether, mixtures thereof, etc.

The maleimido substituted organic polymers utilized in making thesolventless blends of the present invention, can be made by the methodshown by the copending application of Klebe et al., Ser. No.'838,322,filed July 1, 1969 now abandoned, and assigned to the same assignee asthe present invention. The maleimido substituted organic monomers usedin the present invention can be made by the method shown by copendingapplication Ser. No. 103,303, of Klebe et al, filed Dec. 31, 1970 nowUS. Pat. No. 3,789,055, also assigned to the same assignee as thepresent invention.

The above described method of Ser. No. 838,322 now abandoned involvesthe employment of a maleimido alkylating agent such as maleimidomethylchloride and a Friedel Crafts catalyst, such as boron trifluoride incombination with an aromatic carbocyclic polymer defined above. achievedin Ser. No. 103,303 now US. Pat. No. 3,789,055, with a mixture offormaldehyde and an aliphatically unsaturated imide such as maleimide,and sulphuric acid. Water can be employed in particular instances inlimited amounts.

Included by the aromatic organic compounds which can be imido methylatedin accordance with Ser. No. 103,303 now US. Pat. No. 3,789,055 toproduce the imido methyl substituted aromatic carbocyclic monomersutilized in making the solventless resins of the present invention, arearomatic hydrocarbons, such as benzene, biphenyl, naphthalene, andanthracene; alkyl substituted and organo functional substitutedderivatives of such aromatic organic hydrocarbons including toluene,xylene, durene, ethylbenzene, dimethylnaphthalene, benzoic acid, toluicacid, terephthalic acid,

lmidomethylation is I 4,4'-dihydroxybiphenyl, phenylmaleimide, etc.' inaddition, halogen substituted aromatic compounds, such as chlorobenzene,bromonaphthalene, chlorinated biphenyl, etc. Diphenyl compounds, such asdiphenyl ether, diphenyl sulfone, diphenyl carbonate, diphenyl methane,and 2,2-diphenyl propane.

The above described blends of maleimide substituted aromatic carbocyclicmaterials and'vinyl ethers can contain non-volatile components such asultraviolet radiation photosensitizers, for example, ketones such asbenzophenone, acetophenone, benzil, benzyl methyl ketone; benzoins andsubstituted benzoins such as benzoin methyl ether, a-hydroxymethylbenzoin isopropyl ether; halogen containing compounds such asa-bromoacetophenone, p-bromoacetophenone, achloromethylnaphthalene,sulfur compounds such as thiurammono and disulfides, or aromaticdisulfides, and other photosensitizers such as azides, thioketones, ormixtures thereof; stabilizers, antioxidants and ultraviolet stabilizerssuch as hydroquinone. tert-butyl hydroquinone. tert butyl catechol,p-benzoquinone, 2,. diphenylbenzoquinone, 2.o-di-tert-butyl-p-cresol,benzotriazoles such as Tinuvin P, Tinuvin 328 (manufactured by GeigyCorp. hydroxybenzophenones such as 2,4-dihydroxy-benzophenone,2-hydroxy-4-methoxybenzophenone, 4-dodecyl-2-hydroxybenzophenone,substituted acrylonitriles such as, ethyl-2-cyano-3,3- diphenylacrylate, 2-ethylhexyl-2-cyano-3,3-diphenyl acrylate, etc.; variousfillers flatting agents, thixotroptic agents, dyes and pigments such as,barytes, blanc fixe,

gypsum, calcium carbonates, quartz, diatomaceous silica, syntheticsilica, clay, talc, asbestine, mica, bentonite, aerogels, glass fibers,basic carbonate white lead, antimony oxide, lithophone, titaniumdioxide, ultramarine blue, aluminum powder, etc.

Blends of the present invention can readily be made by merely mixingtogether the maleimido substituted aromatic carbocyclic organicmaterial, the vinyl organic ether and the above described non-volatilecomponents. The sensitizer can be present at 0.1 to 5 percent byweightof the blend; fillers can be present at from 1 to 60 percent by weightof the blend and stabilizers can be present at from 0.2 to 4 percent byweight of the blend.

As shown in copending application Ser. No. 164,624, now abandoned of A.N. Wright and S. Schroeter, filed concurrently herewith and. assigned tothe same assignee as the present invention, the solventless blends ofthe present invention can be converted to high performance films andcoatings on a variety of substrates to impart improved characteristicsthereto when exposed to ultraviolet radiation.

in order that those skilled in the art will be better able to practicethe invention, the following examples are given by way of illustrationand not by way of limitation. All parts are'by weight.

EXAMPLE 1 A mixture of 97 parts of maleimide, and 60 parts ofparaformaldehyde was dissolved in parts of 97.8 percent sulfuric acid,and 32.5 parts of water was added. The mixture was allowed to cool to45C. There was added to the mixture 138 parts of toluene, and themixture was stirred. The temperature of the mixture was maintained at50C during addition. After 2 hours, 15 parts of paraformaldehyde wasadded and stirring of the mixture continued at 50C for an additionalperiod of 4 hours. A white viscous emulsion formed during the reaction.it was broken by addition of approximately 250 parts of water and about375 parts of chloroform. The organic layer was separated, washed withdilute sodium bicarbonate solution and water, and dried. The solvent wasevaporated and a yellow viscous fluid was extracted with three 33 partportions of hot hexane. After removal of residual solvent -in-vacuo at50C, there was obtained 186 parts of product. The product converted to athermoplasticsolid when allowed to cool at room temperature. The NMRspectrum of the product showed an average of 3 toluene rings, twomaleimidomethyl groups and two methylene bridges between rings.Elemental analysis (wt. percent) showed: C 73.4; H 5.8; N 4.7, and amolecular weight of 500:5 percent.

Based on method of preparation and analytical data, the productwas-composed of two maleimido methyl radicals and three tolylene groups,interconnected by slide, and exposed for 3 minutes under a GeneralElectric H3T7 medium pressure mercury lamp. The transparent filmexhibited valuable solvent resistant properties.

EXAMPLE 2 A solventless resin blend was prepared by dissolving 1.55parts of the bis(imidomethyl) toluene of Example 1, with 08 part ofdiethylene glycol divinyl ether. The resulting blend was cured to a hardtransparent film when it was applied onto a glass slide and exposedunder a 275 watt General Electric sunlamp for about 5 minutes. The filmwas insoluble in organic solvent such as acetone, benzene, orchloroform.

EXAMPLE 3 A blend consisting of the bis(imidomethyl)toluene of Example land diethylene glycol divinyl ether was prepared utilizing 3.1 parts ofthe bis(imidomethyl)toluene and 1.582 parts of the diethylene glycoldivinyl ether along with 0.03 part of benzophenone. A cured film wasfound to be insoluble in organic solvent, such as acetone, benzene andchloroform as well as exhibiting a pencil hardness of greater than 6Hwhen cured under a 275 watt General Electric sunlamp for 5 minutes.

EXAMPLE 4 A blend of the bis(imidomethyl)toluene of Example l anddiethylene glycol divinyl ether was prepared utilizing 3.1 parts of thebis(imidomethyl)toluene and 1.582 parts of the ether in combination with0.03 part of benzophenone. The resulting composition was employed on apolycarbonate panel, which was made from a commercially availablepolycarbonate resin utilizing enough of the solventless resin to producea film having a thickness of about 3 mil. The film was cured under aGeneral Electric H3T7 lamp to give a hard transparent coating whichcould be wiped with acetone, benzene, or chloroform, without showing aneffect on the polycarbonate substrate.

EXAMPLE 5 EXAMPLE 6 There was blended 2 parts of the bis(imidomethyl)toluene of Example 1 and 0.4 part of a maleimido methyl substitutedpolycarbonate. with a mixture of 0.8

, part of phenyl vinyl ether, 0.66 part of styrene and 0.5

part of diethylene glycol divinyl ether.

The maleimidomethyl substituted polycarbonate was prepared by reacting0.27 part of N-chloromethyl maleimide with 5 parts of a commerciallyavailable 6 polycarbonate prepared from 2,2-bis(4-hydroxyphenyl)propanehaving an intrinsic viscosity in dioxane of 25C of about 0.5. Thevarious reactants were dissolved in parts of anhydrous mixtureconsisting of about 70 parts of tetrachloroethane and 30 parts ofnitrobenzene, boron trifluoride was introduced into the mixture while itwas stirred at a rate of one bubble per second over a period of about 50hours, while the temperature was maintained at about 65C. A quantitativeyield of product was then recovered by precipitation with methanol.Based on method of preparation and elemental analysis, the product was amaleimido methyl substituted polycarbonate having about 25 mole percentof maleimidomethyl substituted bisphenol-A carbonate units.

The above solventless blend was applied to a paint test panel and curedunder a General Electric H3T7 lamp for about 5 minutes. There wasobtained a cured film exhibiting excellent adhesion and flexibilitywhich was resistant towards acetone, chloroform, benzene and hot water.The film became yellow after being heated in air to C for 60 hours, butstill retained good adhesion to the test panel.

Although the above examples are limited to only a few of the very manyblends included within the scope of the present invention, it should beunderstood that the present invention is directed to blends comprising amuch broader variety of vinyl organic ether of formula 2 and aromaticcarbocyclic organic materials substituted with radicals of formula 1.

I claim:

l. Solventless blend which consists essentially of, (A) a maleimidomethyl substituted toluene having an average of 3 toluene rings and atleast two chemically combined maleimido radicals of the formula,

ll XC C 7 /NR'' 2 XC C and (B) a vinyl ether of the formula,

' cri=cH,oY,

phatically unsaturated ether is phenyl vinyl ether.

1. SOLVENTLSS BLEND WHICH CONSISTS ESSENTIALLY OF, (A) A MALEIMIDOMETHYL SUBSTITUTED TOLUENE HAVING AN AVERAGE OF 3 TOLUENE RINGS AND ATLEAST TWO CHEMICALLY COMBINED MALEIMIDO RADICALS OF THE FORMULA,
 2. Ablend in accordance with claim 1, where the aliphatically unsaturatedether is diethylene glycol divinyl ether.
 3. A blend in accordance withclaim 1, where the aliphatically unsaturated ether is phenyl vinylether.